Crystal structures of [Cu(phen)(H2O)3(MF6)]·H2O (M = Ti, Zr, Hf) and [Cu(phen)(H2O)2F]2[HfF6]·H2O

The crystal structures of three bridged bimetallic mol­ecular compounds, namely, tri­aqua-2κ3O-μ-fluorido-penta­fluorido-1κ5F-(1,10-phenanthroline-2κ2N,N′)copper(II)titanium(IV) monohydrate, [Cu(TiF6)(phen)(H2O)3]·H2O (phen is 1,10-phenanthroline, C12H8N2), (I), tri­aqua-2κ3O-μ-fluorido-penta­fluorido-1κ5F-(1,10-phenanthroline-2κ2N,N′)copper(II)zirconium(IV) monohydrate, [Cu(ZrF6)(phen)(H2O)3]·H2O, (II), and tri­aqua-2κ3O-μ-fluorido-penta­fluorido-1κ5F-(1,10-phenanthroline-2κ2N,N′)copper(II)hafnium(IV) monohydrate, [Cu(HfF6)(phen)(H2O)3]·H2O, (III), and one mol­ecular salt, bis­[diaqua­fluorido­(1,10-phenanthroline-κ2N,N′)copper(II)] hexa­fluorido­hafnate(IV) dihydrate, [CuF(phen)(H2O)2]2[HfF6]·2H2O, (IV), are reported. The bridged bimetallic compounds adopt Λ-shaped configurations, with the octa­hedrally coordinated copper(II) center linked to the fluorinated early transition metal via a fluoride linkage. The extended structures of these Λ-shaped compounds are organized through both intra- and inter­molecular hydrogen bonds and inter­molecular π–π stacking. The salt compound [Cu(phen)(H2O)2F]2[HfF6]·H2O displays an isolated square-pyramidal Cu(phen)(H2O)2F+ complex linked to other cationic complexes and isolated HfF62− anions through inter­molecular hydrogen-bonding inter­actions.